Senior Thesis

Zirconium in Rutile Geothermometry: Peak
Temperature Determination in the Catalina Schist
By Steven Noll
Advisors Dr. Penniston‐Dorland and Dr. Piccoli
GEOL 394
4/27/2015
1

ABSTRACT

Metamorphic rocks in subduction zones are exhumed to the surface by one of two methods:
as coherent packages where rocks moved as a single unit) or as mixed blocks where rocks travel
different paths to the surface. In many mélange zones, the blocks record different peak metamorphic
facies, even on the outcrop scale, suggesting the blocks have moved along different paths within the
subduction zone. Rocks within the Catalina Schist occur in a mélange, however the blocks within a given
region in the field are of a single metamorphic facies. Due to the broad spectrum of pressures and
temperatures at which a metamorphic facies can form, the question becomes whether or not the blocks
within the Catalina Schist mélange might actually record different peak temperatures of formation. The
zirconium content of rutile grains within four samples of varying lithologies from a single outcrop of the
Catalina Schist were analyzed by using an electron probe microanalyzer in order to determine whether
the Catalina Schist shows evidence of rock mixing or of rocks moving together as a package. The
zirconium content of rutiles is used to calculate the peak temperature of recrystalization each sample by
using the zirconium in rutile geothermometer. If the rocks record evidence for significantly different
peak temperatures (outside of two sigma uncertainty of standard deviation of mean), it will suggest that
they moved along different paths within the subduction zone. The calculated temperatures of the four
samples have been compared to determine whether or not they likely reached different peak
temperatures. I have performed petrography and analyzed rutiles from all four of the samples from the
outcrop. The zirconium content used in the calculation of the temperature for each sample came from
the maximum zirconium concentrations found in the centers of the crystals. The average zirconium
concentrations measured within the cores of the rutiles of the samples range from 242 to 473 ppm.
These concentrations lead to a calculated temperature range of 633°C to 687°C at 10 kbar (using the
calibration of Tomkins et al., 2007) across all the samples. The uncertainty calculated by finding the
standard deviation of mean (2σ) was approximately 20°C across all the samples. The final calculated
temperatures of the samples fell within uncertainty of each other, supporting the model that these
rocks moved through the subduction zone as a cohesive package.
2

INTRODUCTION
Subduction zones occur where two tectonic plates, one oceanic and one either oceanic or
continental, converge and the oceanic plate subducts into the mantle beneath the overriding plate.
Volcanoes can form on the overriding plate and earthquakes occur in the area of the subduction zone.
These geologic hazards make subduction zones an important area of study in order to understand the
more violent workings of the earth. Geophysicists can use seismic data to image the crust and mantle
within a subduction zone and geologists can study
rocks formed in volcanoes, however these are
indirect methods of studying subduction zones.
An effective way of gathering information on the
interior of a subduction zone is through the study
of the metamorphic rocks exhumed from the
subduction zone. These metamorphic rocks are
materials that come from inside the subduction
zone and provide evidence for what happens
within a subduction zone. Mélange zones are
thought to represent rocks from the interface
between the down going subducting slab and the
overlying plate, making mélange zones prime
locations for geological study of the processes
Figure 1 Geologic map of Santa Catalina Island. Study area is occurring within subduction zones.
marked by the square. Area in square shown in Figure 3. The primary goal of this project is to
Source: Dr. Sarah Penniston‐Dorland
support a model of rock movement in a
subduction zone. Do they move as a single coherent package or do rocks from one layer break off to
mix with other layers (see figure 2). This model of rocks mixing together in a subduction zone was first
introduced as a model of rocks moving along
different paths within a subduction zone (Cloos,
1982). This mixing process leads rocks to
recrystallize at different depths and therefore
record differing peak temperatures. I will
determine peak temperatures of metamorphic
rocks found in the Catalina Schist. The method I
will use is the zirconium in rutile geothermometer.
The Catalina Schist is a mélange zone off the coast
of California on Santa Catalina Island. The Catalina
Schist contains materials that record P‐T
conditions indicative of subduction zone
environments as well as a mixture of blocks of
material coming from the ultramafic mantle
wedge of the subduction zone and Figure 2 Two models for subduction zones are illustrated.
metamorphosed basaltic and silicic material from Rocks can move as a coherent package (left) or as a mixed
the oceanic crust. The calculated peak package (right). Diagram is modified from Bebout (2007)
temperatures of samples from a single
amphibolite facies outcrop will then be compared. If the temperatures are significantly different, then
the rocks likely did not move as a coherent package. If the peak temperatures are the same, it suggests
they moved as coherent a package.

3

BACKGROUND
There are two endmember models for behavior of rocks within a subduction zone (Bebout
2007), illustrated in figure 2. In the first model, the rocks move together as a cohesive mass during
subduction, with all rocks experiencing approximately the same metamorphic conditions and therefore
the same peak temperatures. In the second model, the rocks do not move together as a cohesive mass
during subduction, with rocks experiencing different metamorphic conditions and therefore different
peak temperatures (Bebout 2007).
The samples I have studied were collected from the Catalina Schist. The Catalina Schist is
located on Santa Catalina Island just off the coast of California near Los Angeles. The rocks in the schist
have been interpreted to represent
rocks that formed in a subduction zone
based on the mineral assemblages.
The metamorphic facies range from
low‐grade lawsonite‐blueschist to high
grade amphibolite. Rocks in the
Catalina Schist occur as coherent
packages in some parts of the
formation and as mélange in other
parts, as can be seen in figures 1 and 3.
These rocks range from 122‐115 million
years in age (Grove et al., 2008). The
Catalina Schist formed when the
Farallon plate subducted under the Figure 3 Geologic map of a portion of the Catalina Schist. Location of
North American plate. Previous samples is illustrated with a star. (Dr. Sarah Penniston Dorland)
pressure and temperature estimates for the amphibolites in the Catalina Schist are approximately 8‐11
kbar and 640‐750°C respectively, see figure 4 (Bebout, 2007; Sorensen and Barton, 1987). The rocks
used for this project were taken from the sample location
in figure 3.
The Catalina Schist exhibits a narrower range of
metamorphic facies found within a region of mélange
compared to another nearby suite of subduction‐related
metamorphic rocks, the Franciscan Complex, which
exhibits a wide range of metamorphic facies in an
exposure of mélange. The Franciscan Complex is located
throughout the California Coast Ranges and the San
Francisco Peninsula. The ages of the rocks found in the
Franciscan Complex range from 150‐65 million years in age
(McLaughlin, 1982). The Franciscan Complex is an example
of the mixing model of subduction zones. Within the
Franciscan Complex one can find blueschist, eclogite, and
garnet amphibolite blocks within the same outcrop. Each
rock records different peak temperatures and pressures
Figure 4 PT diagram illustrating P‐T conditions from each other. Instead of the intense mixing of rock
specific to the amphibolite facies rocks, labeled types of different metamorphic facies within a single
AM, of the Catalina Schist (Bebout, 2007) outcrop, as seen in the Franciscan Complex, the Catalina
Schist has 1‐4 km swaths of outcrops with mixed
lithologies in the same metamorphic facies. The area mapped as amphibolite facies mélange dominated
in figure 3 is an example of this mixing of lithologies in the same metamorphic facies. However, within
4

these facies there is a rather broad spectrum of temperatures and pressures of formation. This brings
forward the question that I am attempting answer: do the rocks in the Catalina Schist mix together in
the subduction zone or move together as a single package? I measured the zirconium content of rutile
in four different Catalina Schist metamorphic rocks from a single outcrop. My hypothesis is that the
zirconium content of the rutile will be significantly different in each of these rocks. This would suggest
that the rocks in the Catalina Schist did not move as a coherent single package.

METHODS
Figure 5 Garnet Quartzite A sample Figure 6 Garnet Mica Schist sample
Figure 7 Garnet Quartzite B sample Figure 8 Garnet Amphibolite sample
In order to test my hypothesis I studied 4 samples from the Catalina Schist. These samples were
taken from a single outcrop area approximately 100 square meters in area as marked by the star in
figure 3. The samples have different lithologies and are a good representation of the rocks that can be
found throughout the Catalina Schist. The four samples that I examined are a garnet amphibolite
(sample A14‐64F), two garnet quartzites (samples A14‐64F and A14‐64E), and a garnet mica‐schist
(sample A14‐64D). The rutile was identified and mapped with the petrographic microscope before rutile
was analyzed. To determine the zirconium content of the rutiles, I used the Electron Probe
Microanalyzer. I performed traverses across larger grains to check for zoning. To detect zoning in
smaller rutile grains, analyses of grain cores and rims were performed. The concentration of zirconium
oxide (ZrO2) in rutile was then used to calculate a temperature. If the rutiles in different samples yield a
large difference in peak temperature they most likely recrystallized at a significant distance from each
other, which would support my hypothesis.
5

I used the zirconium in rutile geothermometer for my temperature calculations. The zirconium
in rutile geothermometer uses the fact that at higher temperatures, zirconium substitutes in higher
concentrations into rutile in place of titanium. Both of these elements have a +4 charge and the atomic
radius for zirconium and titanium are 0.75 and 0.86 angstroms respectively, which allows zirconium to
easily fit into the space that titanium would normally occupy in the bond. The use of this thermometer
requires the presence of rutile, zircon, and quartz, (for an example of these phases see figure 9). All
samples used in this experiment have the required phases for this geothermometer. The equilibrium
reaction is ZrSiO4 + TiO2 ‐> ZrO2 (in rutile) +SiO2. Using the zirconium concentrations measured in rutile,
a peak temperature can be calculated using (for samples containing alpha quartz):
83.9 .410
° 273
. 1428 ln ф
where ф is ppm, P is the pressure experienced by the sample, and R is the gas constant, 0.0083144 kJ/K
(Tomkins et al., 2007). Tomkins et al (2007) performed a series
of experiments where pure TiO2 was made to take up ZrO2
until it approached equilibrium with coexisting zircon and
quartz, and made ZrO2 rich rutile give up ZrO2 until it Muscovite
approached equilibrium with coexisting zircon and quartz, Zircon
called forward and reversal experiments respectively. These
experiments were conducted at temperatures of 1000‐1500 °C
Garnet
and at 1, 2, and 3 GPA. The experiments were then calibrated
to results from empirical studies so that they can be applied to Quartz
rocks that experienced lower temperatures. For the purposes
of these calculations, I used pressures estimated for these Rutile
rocks, ranging from 0.8‐1.1 GPa consistent with the pressure 175 microns
estimates of Sorensen and Barton (1987). The reason I am
using the alpha quartz calibration is because, at the pressures I
used, the calculated temperatures of the rutile crystals that I Figure 9 Back Scattered Electron image of
have analyzed (see Data section) are below 800 °C which is in rutile, quartz, and zircon in the same area as
the stability field of alpha quartz at the pressure of interest. each other for zirconium substitution in
Analyses were performed on a JEOL JXA 8900 electron rutile. Other minerals are noted as well.
probe microanalyzer. An accelerating voltage of 20 kV and cup
current of 120 nA were used. The following standards were used: synthetic zircon (Zr, Si), rutile (Ti),
Bushveld Chromite (Al, Fe), Ilmen Mountains Ilmenite (Mn), and pure metal standards (Nb, Ta). Count
times for Zr were 300 seconds on peak and 150 on each background. Zr was measured on a high‐
intensity PETH crystal (on a small diameter Rowland circle spectrometer). An asymmetric background
was used (‐2/+3 mm) to model the Zr peak. The detection limit for Zr was 20‐25 ppm (Appendix, pg 13)
Measurements that were clearly not 100% rutile were excluded from consideration for
calculations. To determine the measurements that fell outside of usable criteria I considered the total
weight percent of each measurement and the amount of silicon measured. All measurements that were
outside of 100% +/‐2% total weight percent were excluded. All measurements that had more than 300
parts per million of silicon were also excluded. I followed the methods of McBride (2013) for these
criteria.
The uncertainty for the zirconium measurements in these analyses is estimated from counting
statistics from the electron probe microanalyzer and reported at the 2‐sigma level. These counts
assumed a Gaussian curve along which the measurements fell to give an uncertainty for each
measurement.

DATA
6

The first sample analyzed was the larger of the two garnet quartzites, garnet quartzite A, sample
A14‐64B. The rutiles in this particular sample are sparse, approximately 1% volume of rutile in the rock,
estimated from the thin section. However what this sample lacks in number of rutile crystals it makes
up for in crystal size. The largest rutile crystals in this sample are 3000 micrometers across. As stated
earlier in the paper, I have gathered traverse analyses across the larger crystals and edge and core
analyses of the smaller crystals. I have analyses from 6 rutile crystals for this sample. The results can be
found in Appendix table 1.
Garnet Quartzite A ‐ Crystal A
600.0
Zirconium Content (ppm)
500.0
400.0
300.0
200.0
100.0
0.0
0.0 500.0 1000.0 1500.0 2000.0 2500.0 3000.0
Distance Across Crystal (micrometers)

Figure 10 Zirconium content of crystal A of Garnet Quartzite A. Red lines indicate the 2 sigma standard deviation of mean
and the blue line indicates calculated average of zirconium content for this crystal. Black error bars on each data point
represent 2 sigma uncertainty for each measurement based on Electron Probe Microanalyzer counting statistics.

The zirconium content measured in the crystals in this sample ranges from 110 parts per million
to 499 ppm. Many of the lower concentration measurements were analyses that had silicon
concentrations greater than 300 ppm and were not included in the averages. As the graphs show, the
zirconium content is higher in the cores of the crystals than at the rims (figures 9, 14‐18). The average
zirconium content of these crystals was calculated from the measurements that fell within analytical
uncertainty of each other and with silicon concentrations less than 300 ppm. In the majority of the
crystals these measurements came from the cores of the crystals. The uncertainty of zirconium
concentration of the crystal was then calculated using the standard deviation of mean of the same
measurements used in calculating the average zirconium content of the crystal.
The rutiles in the garnet mica schist, while more abundant in number than the rutiles in the first
garnet quartzite, were also far smaller, thereby having a much lower volume in the rock. There is less
than .5% volume of rutile in the rock. The rutiles in this sample range from 71 microns across to 152
microns across according to measurements of the traverses across the crystals done by the EPMA. I
measured the zirconium content of the grains in spots along line traverses across all the analyzed rutiles
in this sample. I analyzed five rutile crystals in this sample. One sample traverse is illustrated in figure
10.
7

Garnet Mica Schist‐Crystal E
500
450
400
350
300
250
200
150
100
50
0
0 10 20 30 40 50 60 70 80
Distance across Crystal (micrometers)

Figure 11 Zirconium content of crystal E of garnet mica schist. Red lines indicate the 2 sigma standard deviation of mean and
the blue line indicates calculated average of zirconium content for this crystal. Black error bars on each data point represent
2 sigma uncertainty for each measurement based on Electron Probe Microanalyzer counting statistics.
The zirconium content in these crystals ranges from 170 parts per million to 435 parts per
million. The rutiles in this sample also have lower zirconium contents in the rims than in the cores of the
crystals. Crystal B has two analyses with low zirconium concentrations in the center of the crystal, but
this is most likely caused by the fact that the analyses went over a crack in the crystal as can be seen in
fig 20.
The garnet amphibolite also had more, but smaller, rutile crystals than the garnet quartzite.
There is less than .1% volume of rutile in the rock, and the crystals themselves range from 26
micrometers across to 72 micrometers across. I measured the zirconium content of the grains in spots
along line traverses across all the analyzed rutile crystals in this sample. I have analyses from four of the
crystals in this sample.
8

Garnet Amphibolite‐ Crystal F
350
300
250
200
150
100
50
0
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00

Figure 12 Zirconium content of crystal F of Garnet Amphibolite. Red lines indicate the 2 sigma standard deviation of mean

The zirconium content measured in these crystals range from 211 parts per million to 368 parts
per million. The rutiles have a relatively homogenous zirconium content within uncertainty across the
majority of the sample except for one of the crystals that has lower zirconium content towards the rim.
The last sample that I analyzed was garnet quartzite B (sample A14‐64F). This sample had
sparse rutiles that were rather small. There is only about less than .05% volume of rutile in this rock and
the rutiles range from 28 micrometers to 38 micrometers in length.
Garnet Quartzite B‐Crystal D
500
450
400
350
300
250
200
150
100
50
0
0 5 10 15 20 25 30 35

Figure 13 Zirconium content of crystal D of Garnet Quartzite B. Red lines indicate the 2 sigma standard deviation of mean

The zirconium content measured in these crystals range from 258 parts per million to 415 parts
per million. The rutile crystals in this sample are homogenous, exhibiting little to no zoning and
9

consistent zirconium contents throughout the crystals within uncertainty. The rutiles in this sample
were also all contained within garnets.

DISCUSSION AND CONCLUSIONS
The concentration of the ZrO2 is higher in the cores, relative to the rims of the rutile grains; that
is, the grains are zoned. Zoning can occur when crystals form at or above the closure temperature for
zirconium diffusion in rutile, and some of the zirconium diffuses out of the rutile crystal during cooling.
Using this information, the zirconium content of the cores of the crystals was used to calculate the
approximate peak temperature of formation of each crystal. For each of the crystals analyzed in each
sample, the average zirconium content of the crystal was calculated from the measurements acquired
from the electron probe micro analyzer excluding analyses that were outliers outside of the uncertainty
of measurement and also excluding any analyses that had silicon concentrations greater than 300 ppm.
The uncertainty due to counting statistics was used to determine whether or not a given measurement
was used in the calculation of the average. Analyses with zirconium concentrations outside the
analytical uncertainty of the majority of the analyses were excluded from the calculation of the average.
Outliers, such as the measurements that were on the crack in crystal B of the garnet mica schist and in
the majority of the rims of the crystals, were not included in the measurement of the average. After the
average was calculated for each rutile the standard deviation of the mean of the measurements used in
the average was calculated to find a two sigma uncertainty of the measurements for the crystal.
To calculate the zirconium content for each sample, a similar process to the approach for
individual crystals was used. Crystals that recorded significantly lower zirconium concentrations than
the rest of the crystals in the sample were excluded from the calculation of the average zirconium
content and uncertainty. This affected only the calculations for the garnet mica schist where grain D
had significantly lower zirconium concentrations than the rest of the grains. I used the average
zirconium content for the sample to calculate an average temperature for the sample and used the
standard deviation of mean of the zirconium content to find an uncertainty on the temperature. For
garnet quartzite A, I used an average of the analytical uncertainties to calculate the uncertainty for the
sample since the standard deviation of the mean calculation resulted in an uncertainty that was lower
than the analytical unc ertainty.

Table 2 Average zirconium content calculated for Garnet Mica
Table 1 Average zirconium content calculated for Schist. Grain D fell outside of uncertainty of the rest of the
Garnet Quartzite A measurements and was therefore not used in the calculation
of the average.

10

Garnet Amphibolite
Crystal Average Zr Content Uncertainty
B 338 37
C 280 89
F 249 26
Average 289
SDOM 91
Table 4 Average zirconium content calculated for Garnet
Amphibolite
Table 3 Average zirconium content calculated for Garnet
Quartzite B

The pressure used to calculate the final temperatures was 10 kbar. This falls within the range of
pressures calculated for samples found within the Catalina Schist. (Sorensen and Barton, 1987) I did
calculate the temperatures for different pressures for one sample, however I found that all the
temperature variations are only 3 to 4 degrees Celsius for each kbar of pressure added. This is less than
the uncertainty due to measurement of zirconium concentrations.
Temperature (°C)
Crystal 8 kbar 9 kbar 10kbar 11 kbar
A 678 (671‐683) 682 (675‐688) 687 (680‐692) 691 (684‐697)
B 676 (670‐681) 680 (675‐685) 685 (679‐690) 689 (684‐694)
C 677 (676‐679) 682 (681‐683) 686 (685‐688) 691 (690‐692)
D 676 (669‐683) 680 (674‐688) 685 (678‐692) 689 (683‐697)
E 679 (676‐682) 683 (681‐687) 688 (685‐691) 692 (690‐696)
F 677 (676‐678) 681 (680‐683) 686 (685‐687) 690 (689‐692)
Average 677 681 686 690
Table 5 Temperatures for the average zirconium concentration for six different crystals (A through F) in Garnet Quartzite A
calculated at different pressures. The numbers in parenthesis are the range of temperatures within uncertainty for each
crystal with the average temperature of each crystal outside the parenthesis.
The final calculated temperatures are reported in Table 6:

Table 6 Final Temperatures calculated for all samples at 10 kbar. Temperature is in °C.
11

Figure 14 Final Temperatures of samples. 1 is Garnet Mica Schist, 2 is Garnet Quartzite A, 3 is Garnet Amphibolite, and 4 is
Garnet Quartzite B. Error bars are uncertainty determined by standard deviation of mean of the average zirconium content
of each sample.

Average temperatures for these four rock samples from the same outcrop range from 646 to 686
degrees C. As shown in figure 13, the peak temperatures of all samples fall within uncertainty of each
other. This reflects the fact that average zirconium content of each sample is the same within
uncertainty. These results do not support my hypothesis. This suggests that all of these samples may
have formed at relatively similar temperatures of formation. From this I can conclude that these
samples all may have formed at similar temperatures to each other, thus supporting the single package
model of subduction zone for the Catalina Schist. My calculated temperatures for these samples fell
within the ranges calculated by McBride (2013). The temperatures reported by McBride were 660‐700
°C for the amphibolite facies. The samples analyzed in that study include three amphibolite facies
samples from different localities: an actinolite schist, a garnet amphibolite, and a garnet quartzite. The
calculated temperatures from this study fall within the ranges calculated for the amphibolite facies by
Bebout (2007) which can be seen in figure 4.

12

APPENDIX
The electron probe microanalyzer (EPMA) is an analytical tool used to determine chemical
composition of minerals. It does this by emitting a beam of electrons from a tungsten filament. An
anode plate is charged with 3,000 to 30,000 volts to accelerate the electron beam toward the mineral
being analyzed. The beam is focused using a series of magnetic lenses and apertures to focus the beam
down to a diameter of only a few microns. The filament current determines the resolution of the image
that the EPMA displays and the amount of time it takes to make an analysis. When the electron beam
hits the mineral being analyzed, the mineral gives off x‐rays and secondary electrons. The secondary
electrons and backscattered electrons (incident electrons that have interacted with the sample and lost
some energy) can be used to form an image of the mineral that can be displayed on monitors connected
to the EPMA. The x‐rays can be detected by an energy‐dispersive detector (EDS) and a wavelength
dispersive detector (WDS). Both of these detectors require prior set up to detect specific elements in
the mineral being analyzed. Once this is set up, the EDS can give an immediate display of relative
concentrations of various elements in the mineral being analyzed while the WDS can give highly specific
weight percentages of various elements in the mineral. However in order for the WDS to give accurate
weight percentages of elements within the analyzed mineral, prior analyses must be done on various
samples where the expected amount of a given element is known (standards) in order to calibrate the
EPMA. Details of the operating conditions and the standards used to determine rutile compositions can
be found in the body of the text.
13

Appendix Table 1 All Electron Probe analyses for sample A14‐64B Garnet Quartzite A

14

15

No. TiO2 ZrO2 Al2O3 FeO Nb2O5 SiO2 MnO Ta2O5 Total Comment Distance (μ) Zr Content ppm No. Uncertainty % Zr Uncertainty
5 98.782 0.033 0.018 0.430 0.219 0.005 0.012 0.000 99.5 Line 1 E 5 247 5 7.2 35
6 99.147 0.053 0.021 0.373 0.307 0.001 0.000 0.042 99.9 Line 2 E 14 393 6 4.7 37
8 99.225 0.058 0.018 0.324 0.326 0.006 0.005 0.025 100.0 Line 4 E 22 428 8 4.4 38
9 98.981 0.055 0.023 0.366 0.362 0.001 0.000 0.029 99.8 Line 5 E 31 407 9 4.1 33
10 98.221 0.059 0.017 0.337 0.326 0.004 0.002 0.000 99.0 Line 6 E 39 435 10 4.3 38
11 98.928 0.056 0.022 0.348 0.353 0.013 0.000 0.053 99.8 Line 7 E 48 416 11 4.5 37
12 98.196 0.053 0.015 0.369 0.314 0.010 0.015 0.010 99.0 Line 8 E 57 391 12 4.6 36
13 99.456 0.045 0.030 0.337 0.221 0.007 0.011 0.027 100.1 Line 9 E 65 330 13 5.5 37
14 98.392 0.029 0.061 0.471 0.164 0.079 0.016 0.031 99.2 Line 10 E 74 212 14 8.6 36
15 99.396 0.023 0.024 0.271 0.187 0.034 0.002 0.000 99.9 Line 1 B 4 172 15 10.3 35
16 99.983 0.028 0.020 0.270 0.206 0.013 0.014 0.047 100.6 Line 2 B 11 206 16 7.8 32
17 100.151 0.042 0.020 0.221 0.240 0.011 0.000 0.040 100.7 Line 3 B 19 309 17 5.7 35
18 100.223 0.047 0.021 0.245 0.263 0.005 0.000 0.000 100.8 Line 4 B 26 345 18 5.6 38
19 99.727 0.049 0.036 0.242 0.324 0.000 0.001 0.004 100.4 Line 5 B 34 366 19 4.6 34
20 99.299 0.050 0.025 0.233 0.301 0.010 0.008 0.000 99.9 Line 6 B 41 373 20 5.1 38
21 99.443 0.050 0.031 0.210 0.298 0.009 0.000 0.000 100.0 Line 7 B 48 373 21 4.9 37
22 99.543 0.046 0.019 0.197 0.242 0.015 0.000 0.018 100.1 Line 8 B 56 341 22 5.3 36
Appendix Table 2 All data for Sample A14‐64D Garnet Mica Schist.
23 98.177 0.037 0.371 0.239 0.186 0.685 0.000 0.000 99.7 Line 9 B 63 274 23 6.4 35
24 94.474 0.011 2.133 0.475 0.000 2.913 0.000 0.000 100.0 Line 10 B 71 81 24 16.5 27
25 99.636 0.030 0.016 0.155 0.240 0.016 0.000 0.037 100.1 Line 1 A 3 225 25 8.7 39
26 99.584 0.042 0.017 0.178 0.340 0.000 0.018 0.048 100.2 Line 2 A 18 312 26 5.9 37
27 99.308 0.046 0.036 0.259 0.341 0.021 0.000 0.000 100.0 Line 3 A 32 342 27 5.1 35
28 99.750 0.048 0.013 0.225 0.359 0.003 0.000 0.005 100.4 Line 4 A 47 358 28 5.0 36
29 98.345 0.033 0.022 0.278 0.268 0.000 0.000 0.000 98.9 Line 5 A 61 242 29 6.6 32
30 99.823 0.033 0.020 0.259 0.356 0.009 0.000 0.050 100.5 Line 6 A 76 247 30 7.4 37
31 99.688 0.045 0.015 0.236 0.375 0.005 0.004 0.000 100.4 Line 7 A 91 333 31 5.2 35
32 99.578 0.044 0.028 0.286 0.319 0.006 0.000 0.008 100.3 Line 8 A 105 322 32 5.2 33
33 99.378 0.041 0.022 0.241 0.361 0.013 0.000 0.005 100.1 Line 9 A 120 304 33 6.0 36
34 99.605 0.025 0.014 0.186 0.268 0.207 0.000 0.000 100.3 Line 10 A 134 183 34 8.8 32
35 99.126 0.023 0.025 0.207 0.201 0.040 0.000 0.000 99.6 Line 1 D 3 170 35 10.5 36
36 96.931 0.018 0.524 0.687 0.229 0.758 0.017 0.000 99.2 Line 2 D 11 130 36 16.2 42
37 98.920 0.026 0.042 0.177 0.291 0.039 0.010 0.000 99.5 Line 3 D 19 194 37 10.8 42
38 99.142 0.025 0.027 0.183 0.302 0.030 0.009 0.000 99.7 Line 4 D 27 188 38 8.8 33
39 98.762 0.029 0.030 0.164 0.333 0.040 0.037 0.000 99.4 Line 5 D 35 216 39 7.5 33
40 98.685 0.025 0.025 0.154 0.318 0.029 0.015 0.000 99.3 Line 6 D 44 185 40 10.1 38
41 98.599 0.028 0.043 0.164 0.334 0.026 0.000 0.038 99.2 Line 7 D 52 207 41 7.1 29
42 98.598 0.026 0.029 0.174 0.333 0.018 0.007 0.000 99.2 Line 8 D 60 190 42 9.6 37
43 98.386 0.025 0.025 0.202 0.333 0.031 0.000 0.069 99.1 Line 9 D 68 184 43 9.9 36
45 98.768 0.013 0.069 0.181 0.200 0.085 0.023 0.000 99.3 Line 1 C 3 99 45 24.3 48
46 99.107 0.044 0.032 0.227 0.283 0.006 0.000 0.000 99.7 Line 2 C 20 323 46 5.8 37
47 99.013 0.040 0.024 0.272 0.343 0.001 0.018 0.045 99.8 Line 3 C 36 296 47 6.0 35
48 99.632 0.038 0.026 0.273 0.334 0.006 0.033 0.019 100.4 Line 4 C 53 280 48 6.5 36
49 99.010 0.051 0.022 0.239 0.327 0.006 0.009 0.022 99.7 Line 5 C 69 376 49 4.7 35
50 99.534 0.034 0.030 0.207 0.297 0.017 0.037 0.045 100.2 Line 6 C 86 248 50 7.3 36
51 99.296 0.024 0.030 0.176 0.296 0.022 0.000 0.000 99.8 Line 7 C 102 176 51 10.0 35
52 99.263 0.020 0.029 0.195 0.219 0.023 0.000 0.020 99.8 Line 8 C 119 150 52 10.9 33
53 98.604 0.025 0.028 0.181 0.248 0.025 0.005 0.000 99.1 Line 9 C 135 183 53 10.4 38

16

56 98.024 0.043 0.071 0.832 0.078 0.119 0.143 0.011 99.3 Line 2 A 6 316 56 5.5 35
57 98.299 0.050 0.069 0.722 0.096 0.049 0.140 0.000 99.4 Line 3 A 11 370 57 4.9 36
58 98.204 0.051 0.079 0.627 0.102 0.065 0.089 0.000 99.2 Line 4 A 15 380 58 4.9 37
59 97.768 0.051 0.077 0.641 0.065 0.053 0.071 0.000 98.7 Line 5 A 19 378 59 5.0 38
60 98.060 0.050 0.078 0.588 0.106 0.049 0.053 0.000 99.0 Line 6 A 24 372 60 4.7 35
61 97.937 0.044 0.066 0.615 0.097 0.067 0.050 0.000 98.9 Line 7 A 28 326 61 5.2 34
Appendix Table 3 All data for Sample A14‐64F Garnet Amphibolite.
64 98.566 0.046 0.065 0.696 0.171 0.060 0.113 0.038 99.8 Line 2 B 8 341 64 5.2 35
65 98.672 0.042 0.072 0.631 0.166 0.048 0.095 0.000 99.7 Line 3 B 13 312 65 5.8 36
66 99.332 0.038 0.085 0.604 0.186 0.032 0.074 0.007 100.4 Line 4 B 19 283 66 7.2 41
67 98.992 0.038 0.081 0.555 0.194 0.036 0.069 0.084 100.0 Line 5 B 24 279 67 6.8 38
68 99.722 0.038 0.055 0.569 0.151 0.048 0.088 0.010 100.7 Line 6 B 30 281 68 7.0 39
69 98.541 0.035 0.063 0.605 0.201 0.035 0.086 0.000 99.6 Line 7 B 35 258 69 6.1 31
70 98.393 0.037 0.059 0.700 0.179 0.053 0.088 0.006 99.5 Line 8 B 41 272 70 6.6 36
71 98.448 0.048 0.034 0.751 0.081 0.045 0.107 0.000 99.5 Line 1 C 2 352 71 5.6 40
72 97.971 0.038 0.061 0.657 0.088 0.058 0.089 0.014 99.0 Line 2 C 7 278 72 5.7 32
73 98.433 0.039 0.060 0.615 0.060 0.062 0.134 0.000 99.4 Line 3 C 12 291 73 6.0 35
74 98.727 0.042 0.029 0.541 0.069 0.036 0.055 0.050 99.5 Line 4 C 16 310 74 5.7 35
75 98.493 0.039 0.029 0.499 0.100 0.058 0.077 0.000 99.3 Line 5 C 21 287 75 6.3 36
76 98.868 0.048 0.051 0.571 0.096 0.050 0.089 0.027 99.8 Line 6 C 26 352 76 5.0 35
77 98.312 0.045 0.042 0.637 0.072 0.065 0.136 0.000 99.3 Line 7 C 31 329 77 5.5 36
79 98.360 0.049 0.102 0.911 0.326 0.054 0.150 0.000 100.0 Line 1 D 3 362 79 4.8 35
80 98.535 0.048 0.115 0.761 0.315 0.057 0.107 0.000 99.9 Line 2 D 8 358 80 4.8 34
81 98.791 0.052 0.124 0.756 0.332 0.040 0.081 0.032 100.2 Line 3 D 13 387 81 4.4 34
82 98.992 0.051 0.122 0.722 0.325 0.028 0.108 0.067 100.4 Line 4 D 18 377 82 4.5 34
83 98.189 0.055 0.132 0.690 0.339 0.038 0.052 0.000 99.5 Line 5 D 23 405 83 4.7 38
84 97.509 0.052 0.122 0.763 0.347 0.050 0.099 0.090 99.0 Line 6 D 28 381 84 4.6 35
85 97.324 0.051 0.107 0.837 0.311 0.035 0.126 0.034 98.8 Line 7 D 33 381 85 4.6 35
87 97.980 0.053 0.056 0.702 0.114 0.047 0.135 0.000 99.1 Line 1 E 3 393 87 4.8 38
88 98.841 0.056 0.054 0.707 0.125 0.063 0.087 0.000 99.9 Line 2 E 7 415 88 4.4 36
89 98.363 0.052 0.058 0.645 0.145 0.047 0.097 0.035 99.4 Line 3 E 10 388 89 4.3 33
90 98.262 0.052 0.049 0.677 0.126 0.053 0.085 0.000 99.3 Line 4 E 14 388 90 4.3 34
91 98.930 0.055 0.042 0.640 0.142 0.045 0.071 0.000 99.9 Line 5 E 17 409 91 4.3 35
92 98.177 0.050 0.040 0.647 0.126 0.046 0.105 0.000 99.2 Line 6 E 21 369 92 5.0 37
93 98.862 0.047 0.043 0.675 0.117 0.055 0.119 0.034 100.0 Line 7 E 25 349 93 4.8 33

17

105 98.147 0.045 0.023 0.263 0.040 0.065 0.000 0.021 98.6 Line 1 B 2.00 331 105 5.7 38
106 97.736 0.050 0.019 0.233 0.031 0.039 0.000 0.014 98.1 Line 2 B 7.93 368 106 5.3 39
Appendix Table 4 All data for Sample A14‐64G Garnet Quartzite B.
107 98.198 0.043 0.020 0.241 0.043 0.029 0.000 0.056 98.6 Line 3 B 13.86 315 107 6.1 38
108 98.338 0.045 0.019 0.231 0.041 0.014 0.013 0.000 98.7 Line 4 B 19.79 334 108 5.0 33
109 97.871 0.048 0.026 0.230 0.070 0.015 0.000 0.000 98.3 Line 5 B 25.72 352 109 5.6 40
110 97.827 0.044 0.018 0.235 0.044 0.027 0.000 0.000 98.2 Line 6 B 31.65 329 110 6.0 39
111 98.670 0.029 0.025 0.186 0.029 0.016 0.010 0.000 99.0 Line 7 B 37.58 211 111 8.3 35
112 97.705 0.032 0.025 0.211 0.059 0.026 0.000 0.000 98.1 Line 8 B 43.51 240 112 7.7 37
118 98.127 0.035 0.029 0.183 0.049 0.027 0.002 0.000 98.5 Line 4 C 23.60 261 118 6.9 36
119 98.235 0.048 0.025 0.204 0.058 0.020 0.035 0.000 98.6 Line 5 C 30.80 355 119 5.4 38
120 98.187 0.039 0.021 0.204 0.034 0.020 0.000 0.000 98.5 Line 6 C 38.00 285 120 5.9 34
122 99.704 0.034 0.014 0.182 0.044 0.023 0.015 0.051 100.1 Line 8 C 52.40 254 122 6.8 35
123 99.364 0.033 0.029 0.210 0.040 0.029 0.000 0.035 99.7 Line 9 C 59.60 245 123 7.8 38
125 99.619 0.026 0.034 0.246 0.049 0.124 0.015 0.091 100.2 Line 1 F 3.00 196 125 11.4 44
126 98.859 0.031 0.026 0.272 0.047 0.069 0.008 0.021 99.3 Line 2 F 9.90 226 126 8.7 39
127 99.106 0.035 0.034 0.255 0.058 0.051 0.000 0.019 99.6 Line 3 F 16.80 256 127 7.0 36
128 100.048 0.033 0.029 0.294 0.031 0.049 0.000 0.053 100.5 Line 4 F 23.70 245 128 8.1 40
129 100.301 0.036 0.029 0.282 0.052 0.036 0.000 0.000 100.7 Line 5 F 30.60 264 129 6.9 37
130 99.580 0.034 0.026 0.275 0.044 0.041 0.000 0.000 100.0 Line 6 F 37.50 250 130 7.4 37
131 100.042 0.031 0.021 0.289 0.033 0.048 0.022 0.014 100.5 Line 7 F 44.40 229 131 8.3 38
132 99.737 0.034 0.031 0.265 0.046 0.072 0.003 0.000 100.2 Line 8 F 51.30 253 132 7.6 39
133 100.312 0.039 0.030 0.280 0.046 0.167 0.016 0.000 100.9 Line 9 F 58.20 292 133 6.2 36
135 99.356 0.034 0.019 0.289 0.068 0.165 0.004 0.000 99.9 Line 1 G 1.00 253 135 7.6 38
136 99.820 0.023 0.013 0.277 0.059 0.164 0.000 0.042 100.4 Line 2 G 3.96 170 136 9.1 31
137 100.212 0.028 0.013 0.303 0.027 0.144 0.000 0.000 100.7 Line 3 G 6.92 208 137 8.6 36
138 100.394 0.032 0.020 0.323 0.039 0.122 0.000 0.000 100.9 Line 4 G 9.88 240 138 8.0 38
139 99.458 0.033 0.016 0.292 0.031 0.139 0.000 0.000 100.0 Line 5 G 12.84 242 139 6.5 31
140 99.962 0.038 0.023 0.276 0.035 0.165 0.026 0.022 100.5 Line 6 G 15.80 280 140 7.0 39
141 100.030 0.035 0.026 0.294 0.030 0.218 0.013 0.022 100.7 Line 7 G 18.76 258 141 6.7 35
142 99.631 0.038 0.021 0.242 0.063 0.302 0.039 0.000 100.3 Line 8 G 21.72 285 142 7.1 40

Appendix Figure 1 Zirconium content of crystal B of Garnet Quartzite A. Red lines indicate the 2 sigma standard deviation of
mean and the blue line indicates calculated average of zirconium content for this crystal.
Appendix Figure 2 Zirconium content of crystal C of Garnet Quartzite A. Red lines indicate the 2 sigma standard deviation of mean and
the blue line indicates calculated average of zirconium content for this crystal. Measurements 1 and 4 are rim analyses and 18

measurements 2 and 3 are core analyses. Black error bars on each data point represent 2 sigma uncertainty for each measurement
based on Electron Probe Microanalyzer counting statistics.

Appendix Figure 3 Zirconium content of crystal C of Garnet Quartzite A. Red lines indicate the 2 sigma standard deviation of
mean and the blue line indicates calculated average of zirconium content for this crystal. Measurements 1, 4 and 5 are rim
analyses and measurements 2 and 3 are core analyses. Black error bars on each data point represent 2 sigma uncertainty for
each measurement based on Electron Probe Microanalyzer counting statistics.
mean and the blue line indicates calculated average of zirconium content for this crystal. Measurements 1, 5 and 6 are rim
19

analyses and measurements 2, 3, and 4 are core analyses. Black error bars on each data point represent 2 sigma uncertainty
for each measurement based on Electron Probe Microanalyzer counting statistics.

mean and the blue line indicates calculated average of zirconium content for this crystal. Measurements 1 and 5 are rim
analyses and measurements 2, 3, and 4 are core analyses. Black error bars on each data point represent 2 sigma uncertainty
for each measurement based on Electron Probe Microanalyzer counting statistics.
20

Appendix Figure 6 Zirconium content of crystal A Garnet Mica Schist. Red lines indicate the 2 sigma standard deviation of
mean and the blue line indicates calculated average of zirconium content for this crystal. Black error bars on each data point

Appendix Figure 7 Zirconium content of crystal B of Garnet Mica Schist. Red lines indicate the 2 sigma standard deviation of
21

Appendix Figure 8 Zirconium content of crystal C of Garnet Mica Schist. Red lines indicate the 2 sigma standard deviation of
22

Appendix Figure 9 Zirconium content of crystal D of Garnet Mica Schist. Red lines indicate the 2 sigma standard deviation of
Appendix Figure 10 Zirconium content of crystal A of Garnet Quartzite B. Red lines indicate the 2 sigma standard deviation of
23

Appendix Figure 11 Zirconium content of crystal B of Garnet Quartzite B. Red lines indicate the 2 sigma standard deviation of
Appendix Figure 12 Zirconium content of crystal C of Garnet Quartzite B. Red lines indicate the 2 sigma standard deviation of
24

Appendix Figure 13 Zirconium content of crystal E of Garnet Quartzite B. Red lines indicate the 2 sigma standard deviation of
25

Appendix Figure 14 Zirconium content of crystal B of Garnet Amphibolite. Red lines indicate the 2 sigma standard deviation
of mean and the blue line indicates calculated average of zirconium content for this crystal. Black error bars on each data
point represent 2 sigma uncertainty for each measurement based on Electron Probe Microanalyzer counting statistics.
26

Appendix Figure 15 Zirconium content of crystal B of Garnet Amphibolite. Red lines indicate the 2 sigma standard deviation
of mean and the blue line indicates calculated average of zirconium content for this crystal. Black error bars on each data
point represent 2 sigma uncertainty for each measurement based on Electron Probe Microanalyzer counting statistics.
27

Start
End
.7 mm

Appendix Figure 17 Garnet Quartzite A crystal A. Line is 415 micrometers long. Dots are beginning and end of analysis run.
15 steps in between, 29.68 micrometers between each step.
28

Start
End
.7 mm

Appendix Figure 18 Garnet Quartzite A crystal B. Line is 154 micrometers long. Dots are beginning and end of analysis run. 6
steps in between, 30.43 micrometers between each step.
29

.7 mm

Appendix Figure 19 Garnet Quartzite A crystal E approximate core and rim analysis locations.
30

.7 mm

Appendix Figure 20 Garnet Quartzite A crystal F. Crystlal is too small to accurately show analysis points.

31

End
Start
.35 mm

Appendix Figure 21 Garnet Mica Schist crystal A. Line is 131.4 micrometers long. 10 steps in between, 14.6 micrometers
between each step.

32

End
Start
.35 mm

Appendix Figure 22 Garnet Mica Schist crystal B. Line is 66 micrometers long. 10 steps in between, 7.4 micrometers
between each step.

33

End
Start
.35 mm

Appendix Figure 23 Garnet Mica Schist crystal C. Line is 148.6 micrometers long. 10 steps in between, 16.52 micrometers
between each step.

34

Start
End
.7 mm

Appendix Figure 24 Garnet Mica Schist crystal D. Line is 76 micrometers long. 10 steps in between, 8.11 micrometers
between each step.

35

Start
End
.7 mm

Appendix Figure 25 Garnet Mica Schist crystal D. Line is 77.3 micrometers long. 10 steps in between, 8.59 micrometers
between each step.

36

.7 mm

Appendix Figure 26 Garnet Quartzite B crystals A. Rutiles are in garnets. Crystals are too small to accurately show analysis
points.

37

.7 mm

Appendix Figure 27 Garnet Quartzite B crystal D. Rutile is in garnet. Crystals are too small to accurately show analysis
points.

38

.7 mm

Appendix figure 28 Garnet Quartzite B crystal E. Rutile is in garnet. Crystals are too small to accurately show analysis points.

39

Start End
End
B Start
C
.35mm

Appendix Figure 29 Garnet Amphibolite crystal B and C. Lines are 53 and 65 micrometers long respectively. 10 steps in
between, 5.93 and 7.2 micrometers respectively between each step.

40

REFERENCES
Bebout, G. E., Metamorphic chemical geodynamics of subduction zones, Earth and Planetary Science
Letters 260, 2007, p 373‐393
Cloos, M., 1982, Flow melanges: Numerical modeling and geologic constraints on the origin in the
Franciscan subduction complex, California, Geological Society of America Bulletin, vol 93, issue 4, 1982,
p. 330‐344
Grove, M., Bebout, G.E., Jacobson, C.E., Barth, A.P., Kimbrough, D.L., King, R.L., Zou, Haibo, Lovera, O.M.,
Mahoney, B.J., Gehrels, G.E., The Catalina Schist: Evidence for middle Cretaceous subduction erosion of
southwestern North America, Geological Society of America Special Papers, 2008, p 335‐361
Mcbride, H., 2013, Zirconium in Rutile Thermometry: Temperature Estimates for Metamorphic Rocks of
the Catalina Schist
McLaughlin, R.J., Kling, S.A., Poore, R.Z., McDougall, K. and Beutner, E.C. (1982). "Post-middle
Miocene accretion of Franciscan rocks, northwestern California". Geological Society of America
Bulletin: v. 93, p. 595–605.
Sorensen, S. S., Barton, M. D., Metasomatism and partial melting in a subduction complex Catalina
Schist, southern California, Geology, 1987, p 115‐118
Tomkins, H.S., Powell, R., Ellis, D.J., 2007, The pressure dependence of the zirconium‐in‐rutile
thermometer, J. metamorphic Geol., 2007, 25, 703–713
41

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Zirconium in Rutile Geothermometry: Peak

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